Materials presently available for protecting vehicles, ammunition, solid, liquid or gaseous fuels, rockets, missiles and/or personnel from small arms projectile penetration or penetration from flying shrapnel, fire, directed energy, explosions and associated heat and the like are relatively expensive. Moreover, such materials do not have self cooling and/or fire extinguishing properties. The composites described herein are relatively inexpensive and cost-effective to manufacture, may be produced in almost any shape, size and thickness, and are recyclable. The composites are configured to release gaseous refrigerant at temperatures above about 150° F. and preferably much higher temperatures, thereby providing cooling and fire extinguishing properties. The composites have mechanical and structural integrity and may be used in conjunction with penetration resistant materials or, in some cases, can be designed to provide some penetration resistance.